WO2014050075A1 - 蓄電池システム。 - Google Patents
蓄電池システム。 Download PDFInfo
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- WO2014050075A1 WO2014050075A1 PCT/JP2013/005630 JP2013005630W WO2014050075A1 WO 2014050075 A1 WO2014050075 A1 WO 2014050075A1 JP 2013005630 W JP2013005630 W JP 2013005630W WO 2014050075 A1 WO2014050075 A1 WO 2014050075A1
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- battery
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- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
- H01M16/00—Structural combinations of different types of electrochemical generators
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- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
- H01M4/00—Electrodes
- H01M4/02—Electrodes composed of, or comprising, active material
- H01M4/36—Selection of substances as active materials, active masses, active liquids
- H01M4/38—Selection of substances as active materials, active masses, active liquids of elements or alloys
- H01M4/383—Hydrogen absorbing alloys
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- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
- H01M10/00—Secondary cells; Manufacture thereof
- H01M10/06—Lead-acid accumulators
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- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
- H01M10/00—Secondary cells; Manufacture thereof
- H01M10/24—Alkaline accumulators
- H01M10/26—Selection of materials as electrolytes
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- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
- H01M10/00—Secondary cells; Manufacture thereof
- H01M10/24—Alkaline accumulators
- H01M10/30—Nickel accumulators
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- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
- H01M10/00—Secondary cells; Manufacture thereof
- H01M10/34—Gastight accumulators
- H01M10/345—Gastight metal hydride accumulators
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- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
- H01M10/00—Secondary cells; Manufacture thereof
- H01M10/42—Methods or arrangements for servicing or maintenance of secondary cells or secondary half-cells
- H01M10/46—Accumulators structurally combined with charging apparatus
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- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
- H01M4/00—Electrodes
- H01M4/02—Electrodes composed of, or comprising, active material
- H01M4/24—Electrodes for alkaline accumulators
- H01M4/242—Hydrogen storage electrodes
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- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
- H01M4/00—Electrodes
- H01M4/02—Electrodes composed of, or comprising, active material
- H01M4/24—Electrodes for alkaline accumulators
- H01M4/32—Nickel oxide or hydroxide electrodes
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- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
- H01M4/00—Electrodes
- H01M4/02—Electrodes composed of, or comprising, active material
- H01M2004/026—Electrodes composed of, or comprising, active material characterised by the polarity
- H01M2004/027—Negative electrodes
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- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
- H01M4/00—Electrodes
- H01M4/02—Electrodes composed of, or comprising, active material
- H01M2004/026—Electrodes composed of, or comprising, active material characterised by the polarity
- H01M2004/028—Positive electrodes
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- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
- H01M2220/00—Batteries for particular applications
- H01M2220/20—Batteries in motive systems, e.g. vehicle, ship, plane
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- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
- H01M2300/00—Electrolytes
- H01M2300/0002—Aqueous electrolytes
- H01M2300/0014—Alkaline electrolytes
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- Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
- Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
- Y02E—REDUCTION OF GREENHOUSE GAS [GHG] EMISSIONS, RELATED TO ENERGY GENERATION, TRANSMISSION OR DISTRIBUTION
- Y02E60/00—Enabling technologies; Technologies with a potential or indirect contribution to GHG emissions mitigation
- Y02E60/10—Energy storage using batteries
Definitions
- the present invention relates to a storage battery system suitable for idling stop applications.
- the nickel metal hydride battery in a storage battery system in which a lead battery and a nickel metal hydride battery are connected in parallel, includes a nickel positive electrode using nickel hydroxide as a main positive electrode active material, and a hydrogen storage alloy.
- a negative electrode active material hydrogen storage alloy negative electrode, a separator, and an alkaline electrolyte are provided in an outer can.
- the hydrogen storage alloy has a general formula of La x Re y Mg 1-xy Nin a M a (re is at least one element selected from rare earth elements including Y (excluding La), M is at least one element selected from other than Co and Mn), and the alkaline electrolyte Is a highly durable storage battery that contains one or more compounds selected from a tungsten compound, a molybdenum compound, and a niobium compound, thereby suppressing the occurrence of an internal short circuit. It is possible to provide a Temu.
- the metal element mass of any one or more compounds selected from the tungsten compound, the molybdenum compound, and the niobium compound contained in the alkaline electrolyte is 20 mg or more and 50 mg or less per 1 g of the alkaline electrolyte
- the amount of sodium (Na) contained in the alkaline electrolyte is preferably 1.0 mol / L or more and 4.0 mol / L or less.
- any of the tungsten compounds, molybdenum compounds, and niobium compounds may be selected in order to suppress this performance degradation.
- One or more compounds were added to the alkaline electrolyte. Thereby greatly improve the charge and discharge durability of ⁇ cell system.
- the nickel positive electrode 11 of the present invention is formed by filling the pores of a nickel sintered substrate serving as a substrate so that the active material has a predetermined filling amount.
- the nickel sintered substrate is prepared as follows. For example, nickel slurry is prepared by mixing and kneading methyl cellulose (MC) as a thickener, polymer hollow microspheres (for example, having a pore size of 60 ⁇ m), and water with nickel powder. Next, after applying nickel slurry to both sides of the punching metal made of nickel-plated steel plate, it is heated at 1000 ° C. in a reducing atmosphere to eliminate the thickener and the polymer hollow microspheres and to burn the nickel powders together. It is produced by tying. The obtained porous nickel substrate was measured with a mercury intrusion porosimeter (Pascal 140 manufactured by Phisons Instruments), and the porosity was 85%.
- the hydrogen storage alloy negative electrode 12 is formed by filling a negative electrode core made of punching metal with a hydrogen storage alloy slurry.
- a hydrogen storage alloy slurry for example, lanthanum (La), neodymium (Nd), magnesium (Mg), nickel (Ni), aluminum (Al) are mixed at a predetermined molar ratio, and this mixture is dissolved in a high frequency induction furnace.
- At least one element general formula La x Re y Mg 1-x -y Ni n-a M a (Re is selected from rare earth elements excluding La: Nd, Sm, Y Etc., an ingot of a hydrogen storage alloy represented by M represents at least one element selected from Al, Co, Mn, and Zn.
- heat treatment was performed for a predetermined time (in this case, 10 hours) at a temperature lower by 30 ° C. than the melting point of the obtained hydrogen storage alloy.
- the obtained hydrogen storage alloy lumps were coarsely pulverized and then the hydrogen storage alloy was mechanically pulverized in an inert atmosphere, and the remaining alloy powder between 400 mesh and 200 mesh was selected by sieving. .
- the particle size distribution was measured with a laser diffraction / scattering type particle size distribution measuring device, the average particle size corresponding to 50% of the mass integral was 25 ⁇ m. This was used as a hydrogen storage alloy powder.
- a mixed aqueous solution prepared by adding potassium hydroxide, sodium hydroxide, and lithium hydroxide to a predetermined molar ratio to which a tungsten compound was added was used.
- tungsten was added so as to be 20 mg to 50 mg per 1 g of the electrolyte.
- an electrolytic solution e was prepared from the electrolytic solution a as shown in Table 1.
- Nickel-hydrogen storage battery The nickel positive electrode 11 and the hydrogen storage alloy negative electrode 12 produced as described above were used, and a separator 13 was interposed between them to form a spiral electrode group. .
- the core exposed part 11c of the nickel positive electrode 11 is exposed at the upper part of the spiral electrode group thus produced, and the core exposed part 12c of the hydrogen storage alloy electrode 12 is exposed at the lower part.
- the negative electrode current collector 14 is welded to the core exposed portion 12c exposed at the lower end surface of the obtained spiral electrode group, and the core exposed portion 11c of the nickel electrode 11 exposed at the upper end surface of the spiral electrode group.
- a positive electrode current collector 15 was welded onto the electrode body to obtain an electrode body.
- the negative electrode current collector 14 was attached to the outer can 17. Welded to the inner bottom. On the other hand, a current collecting lead portion 15 a extending from the positive electrode current collector 15 was welded to the bottom portion of the sealing body 18.
- the sealing body 18 is provided with a positive electrode cap 18a, and a pressure valve (not shown) composed of a valve body 18b and a spring 18c, which are deformed when a predetermined pressure is reached, is disposed in the positive electrode cap 18a.
- Batteries A to G manufactured as described above are charged to 120% of SOC (State Of Charge) at a temperature of 25 ° C. with a charging current of 1 It, and rest for one hour.
- SOC State Of Charge
- the battery A to the battery G were left to stand for 24 hours in a temperature atmosphere at 60 ° C. and then discharged twice in a temperature atmosphere at 30 ° C. until the battery voltage reached 0.9 V with a discharge current of 1 It. Activated.
- Lead battery A lead battery satisfying the following performance was used under the test conditions defined by the Battery Industry Association Standard (SBA S 0101). 5 hour rate capacity: 48Ah Rated cold cranking current: 320A Charge acceptance: 6.0A
- a lead battery has a charging condition defined by the Battery Industry Association Standard (SBA S 0101), that is, a terminal voltage during charging measured every 15 minutes under a charging current of 0.2 It, or an electrolyte density converted to temperature three times. The battery was charged until it showed a constant value, and the open circuit voltage after being allowed to stand at room temperature for 24 hours was measured.
- the nickel metal hydride battery module is charged up to 110% of the battery capacity with a charging current of 1 It, and then the predetermined capacity is discharged at 1 It.
- the open circuit voltage after standing at room temperature for 24 hours is the same as the open circuit voltage of the lead battery. After confirming that it was within 1V, it connected in parallel with the lead battery, and produced the storage battery systems of Comparative Examples 1 and 2 and Examples 1 to 5 shown in Table 2. Further, a lead battery alone was used as Reference Example 1.
- Example 1 In Example 1 in which the battery module C in which the negative electrode alloys Co and Mn were removed from the battery module A was connected in parallel with the lead battery, an improvement in durability nearly twice that of the lead battery alone was confirmed.
- the nickel-metal hydride battery reduces the work of the lead battery. Improved.
- Examples 2 and 3 in which a battery module D in which tungsten was added to the battery module C, and the battery modules E and lead batteries were connected in parallel, durability improvement due to an increase in tungsten up to 50 mg was confirmed.
- tungsten is added, a decrease in charging efficiency during durability is suppressed, and oxygen generation from the positive electrode is reduced. Therefore, it is considered that deterioration of positive and negative electrode materials and increase in resistance are suppressed.
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- Chemical & Material Sciences (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Electrochemistry (AREA)
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- Engineering & Computer Science (AREA)
- Manufacturing & Machinery (AREA)
- Secondary Cells (AREA)
- Battery Electrode And Active Subsutance (AREA)
Abstract
Description
本発明のニッケル正極11は、基板となるニッケル焼結基板の多孔内に活物質が所定の充填量となるように充填されて形成されている。この場合、ニッケル焼結基板は以下のようにして作製されたものを用いている。例えば、ニッケル粉末に、増粘剤となるメチルセルロース(MC)と高分子中空微小球体(例えば、孔径が60μmのもの)と水とを混合、混練してニッケルスラリーを作製する。ついで、ニッケルめっき鋼板からなるパンチングメタルの両面にニッケルスラリーを塗着した後、還元性雰囲気中で1000℃で加熱して、増粘剤や高分子中空微小球体を消失させるとともにニッケル粉末同士を焼結することにより作製される。尚、得られた多孔性ニッケル基板を水銀圧入式ポロシメータ(ファイソンズ インスツルメンツ製 Pascal 140)で測定したところ、多孔度が85%であった。
負極A La0.4Nd0.5Mg0.1Ni3.5(Co,Mn)0.1Al0.1(n=3.7)
負極B La0.4Nd0.5Mg0.1Ni3.5Al0.2(n=3.7)
上述のようにして作製されたニッケル正極11と、水素吸蔵合金負極12とを用い、これらの間に、セパレータ13を介在させて渦巻状に巻回して渦巻状電極群を作製した。なお、このようにして作製された渦巻状電極群の上部にはニッケル正極11の芯体露出部11cが露出しており、その下部には水素吸蔵合金電極12の芯体露出部12cが露出している。ついで、得られた渦巻状電極群の下端面に露出する芯体露出部12cに負極集電体14を溶接するとともに、渦巻状電極群の上端面に露出するニッケル電極11の芯体露出部11cの上に正極集電体15を溶接して、電極体とした。
鉛電池と各ニッケル水素電池モジュールAからGを以下の処理を行ってから並列接続をした。
鉛電池は、電池工業会規格(SBA S 0101)で定める充電条件、すなわち、0.2Itの充電電流で、15分ごとに測定した充電中の端子電圧、または温度換算した電解液密度が3回連続して一定値を示すまで充電し、常温24時間放置後の開回路電圧を測定した。
ニッケル水素電池モジュールは、1Itの充電電流で電池容量の110%までで充電した後、1Itで所定容量を放電し、常温24時間放置後の開回路電圧が、鉛電池の開回路電圧と0.1V以内であることを確認してから鉛電池と並列に接続して、表2に示す比較例1、2、および実施例1から5の蓄電池システムを作製した。また、鉛電池単独を参考例1とした。
(1)評価方法
前記方法により所定開始電圧に調整した鉛電池と、ニッケル水素電池モジュールを並列に接続し、環境温度を60℃として、14Vで60秒の充電と、45Aで59秒の放電と、300Aで1秒の放電とを3600回繰り返した後に、同環境温度で2日間放置する耐久試験を繰り返し行った。
上記の300Aで1秒放電後の電圧が7.2Vを下回ったときの充放電の繰り返し回数を耐久性の指標とし、鉛電池単独の繰り返し回数に対する比率Xを確認した。
今回、特にデータは示さないが、ニオブ化合物、モリブデン化合物においても同様の効果を確認している。
Claims (3)
- 水酸化ニッケルを主正極活物質とするニッケル正極と、水素吸蔵合金を負極活物質とする水素吸蔵合金負極と、セパレータと、アルカリ電解液とを外装体内に備えたアルカリ蓄電池であって、
前記水素吸蔵合金は、一般式がLaxReyMg1-x-yNin-aMa(ReはYを含む希土類元素(Laを除く)から選択される少なくとも1種以上の元素、MはCo、Mn以外から選択される少なくとも1種以上の元素)で表され、前記アルカリ電解液は、タングステン化合物、モリブデン化合物、ニオブ化合物から選択されるいずれか1種以上の化合物を含有し、
前記アルカリ蓄電池が鉛電池と並列に接続されて充放電することを特徴とする蓄電池システム。 - 前記アルカリ電解液に含有するタングステン化合物、モリブデン化合物、ニオブ化合物から選択されるいずれか1種以上の化合物の金属元素質量が、アルカリ電解液1g当たりに、20mg以上、50mg以下で含有されることを特徴とする請求項1に記載の蓄電池システム。
- 前記アルカリ電解液に含有するナトリウム(Na)量が、1.0mol/L以上、4.0mol/L以下であることを特徴とする請求項1又は請求項2に記載の蓄電池システム。
Priority Applications (3)
Application Number | Priority Date | Filing Date | Title |
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US14/415,345 US20150180101A1 (en) | 2012-09-25 | 2013-09-24 | Storage cell system |
JP2014538173A JPWO2014050075A1 (ja) | 2012-09-25 | 2013-09-24 | 蓄電池システム。 |
CN201380043753.4A CN104584313B (zh) | 2012-09-25 | 2013-09-24 | 蓄电池系统 |
Applications Claiming Priority (2)
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JP2012-210314 | 2012-09-25 | ||
JP2012210314 | 2012-09-25 |
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WO2014050075A1 true WO2014050075A1 (ja) | 2014-04-03 |
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PCT/JP2013/005630 WO2014050075A1 (ja) | 2012-09-25 | 2013-09-24 | 蓄電池システム。 |
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US (1) | US20150180101A1 (ja) |
JP (1) | JPWO2014050075A1 (ja) |
CN (1) | CN104584313B (ja) |
WO (1) | WO2014050075A1 (ja) |
Cited By (1)
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CN105895908A (zh) * | 2015-02-16 | 2016-08-24 | 朴力美电动车辆活力株式会社 | 碱性蓄电池的制造方法和碱性蓄电池 |
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CN106602153A (zh) * | 2016-12-27 | 2017-04-26 | 中科泰能高铭科技发展有限公司 | 一种电解液的注入方法 |
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2013
- 2013-09-24 US US14/415,345 patent/US20150180101A1/en not_active Abandoned
- 2013-09-24 JP JP2014538173A patent/JPWO2014050075A1/ja active Pending
- 2013-09-24 CN CN201380043753.4A patent/CN104584313B/zh active Active
- 2013-09-24 WO PCT/JP2013/005630 patent/WO2014050075A1/ja active Application Filing
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JP2013178883A (ja) * | 2012-02-28 | 2013-09-09 | Sanyo Electric Co Ltd | アルカリ蓄電池及びアルカリ蓄電池システム |
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CN105895908A (zh) * | 2015-02-16 | 2016-08-24 | 朴力美电动车辆活力株式会社 | 碱性蓄电池的制造方法和碱性蓄电池 |
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JPWO2014050075A1 (ja) | 2016-08-22 |
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CN104584313B (zh) | 2016-12-28 |
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